JP2019187349A - Withered seashore prevention material - Google Patents

Abstract

To provide a withered seashore prevention material that improves a withered seashore prevention effect.SOLUTION: A withered seashore prevention material is provided which contains cement and a repellent material. It is preferable to contain at least one of a lime nitrogen and a humus acid as the repellent material. Preferably, the usage of the repellent material may be 30-70 pts.mass to total of 100 pts.mass of the cement and the repellent material. Further, it is preferable to contain aggregate and water. Preferably, the usage of the aggregate may be 50-1000 pts.mass to the total of 100 pts.mass of the cement and the repellent material. A concrete structural body is formed by mixing the withered seashore prevention material and hardening it.SELECTED DRAWING: None

Description

The present invention relates to an anti-sunburn material.

There are algae beds where seaweeds grow in coastal waters, and they play an important role for marine organisms such as feeding grounds and spawning grounds. In recent years, however, a phenomenon called “burning fire” has been observed where the seaweed bed disappears. There are various causes of firewood burning, but examples include damage caused by herbivores such as sea urchins and fish, lack of nutrients, etc. (Non-patent Document 1).

In order to improve firewood burning, various techniques relating to the reduction of damage caused by the removal of herbivorous organisms and the supply of nutrient salts for promoting the growth of seaweed have been proposed (Non-Patent Document 1, Patent Documents 1 and 2). 3).

However, even if vegetative organisms are removed, it takes time to recover the algae ground, and even if the growth of seaweeds is promoted, the algae basin recovers temporarily due to the pressure of the vegetative organisms. It has not been improved.
A fertilizer comprising cyanamide and humic acid or a content thereof is described (Patent Document 4). However, there is no description about repellent materials.
A humic acid supplier characterized by mixing a humic acid substance and gypsum and solidifying the mixture is described (Patent Document 5). However, there is no description about cement.

Japanese Patent No. 331339 Japanese Patent No. 5112483 Japanese Patent No. 6086937 JP 2006-342028 A JP 2003-91 A Fisheries Agency, Revised Guidelines for Countermeasures against Burning, 2015

The present invention provides an anti-sunburn material having an improved anti-sunburn effect.

That is, the present invention is a firewood preventing material containing cement and a repellent material, the fireproof material containing at least one of lime nitrogen and humic acid as a repellent material, the sum of cement and repellent material The amount of repellent material used is 30 to 70 parts by weight with respect to 100 parts by weight, and the amount of the material used for the fireproofing material further includes aggregate. The anti-sunburn material is 50 to 1000 parts by mass with respect to a total of 100 parts by mass of cement and repellent material, and further the anti-sunburn material containing water, and the anti-sunburn material is mixed. It is a hardened and molded concrete structure, and is an anti-sunburn material containing cement and a substance containing at least one of lime nitrogen and humic acid.

The anti-burning material of the present invention improves the anti-burning effect.

The concrete of this embodiment is a general term for cement paste, cement mortar, and concrete.
As cement, various portland cements such as normal, early strength, ultra-early strength, low heat, and moderate heat, various mixed cements in which blast furnace slag, fly ash, or silica is mixed with these portland cements, these portland cements, Examples include filler cement mixed with limestone powder, blast furnace slow-cooled slag fine powder, and the like, and environmentally friendly cement (eco-cement) manufactured using municipal waste incineration ash and sewage sludge incineration ash as raw materials. One or more of these can be used.
The cement is preferably ordinary Portland cement. Blaine specific surface area of the cement, preferably 2500~4800cm ² / g, more preferably ^{2800~4000cm 2 / g, 3000~3600cm 2 /} g being most preferred.
The cement preferably contains a cement clinker and gypsum. The cement clinker has a cement mineral composition calculated using the Borg formula. C ₃ S (tricalcium silicate) is 40 to 70% by mass, C ₂ S (dicalcium silicate) is 7 to 40% by mass, C ₃ A ( tricalcium aluminate) 1 to 15% by weight and _C 4 AF (iron aluminate tetracalcium) is preferably 5 to 20 wt%. The content of gypsum in the cement is preferably 0.5 to 4% by mass, more preferably 1.5 to ₃ % by mass in terms of SO ₃ .

As the repellent material, a substance having a repellent effect on herbivores such as sea urchins is preferable. As the repellent material, a substance having an effect of preventing firewood burning is preferable. As a substance having an effect of preventing firewood burning, it is more preferable to contain at least one of lime nitrogen and humic acid, and it is most preferable to use lime nitrogen and humic acid in combination. As the repellent material, lime nitrogen is preferable in terms of strength development. As the repellent material, humic acid is preferable from the viewpoint of the growth of seaweed.
When lime nitrogen and humic acid are used in combination, the usage ratio of lime nitrogen and humic acid is lime nitrogen: humic acid = 10-90 parts by mass: 10-90 parts by mass in a total of 100 parts by mass of lime nitrogen and humic acid. Preferably, 30 to 70 parts by mass: 30 to 70 parts by mass is preferable, and an equivalent amount is most preferable.

As lime nitrogen, generally available lime nitrogen is sufficient. Lime nitrogen, a main component of calcium cyanamide (CaCN _2), quicklime (CaO), slaked lime (Ca _(OH) 2), although materials such as a carbon (C) or the like subcomponents are known, CaCN ₂ Any of those containing 40% by mass or more can be used. The average particle diameter is preferably from 0.01 to 0.4 mm, more preferably from 0.05 to 0.3 mm.

The shape and component concentration of lime nitrogen are not particularly limited as long as the concrete structure can be hardened or molded. Cyanamide and calcium oxide contained in lime nitrogen have a repellent effect on herbivorous and other herbivorous organisms and suppress food pressure on seaweed. Since cyanamide is gradually degraded in the environment, there is no concern about environmental contamination due to residual cyanamide. Cyanamide nitrogen is converted to ammonia nitrogen or nitrate nitrogen via urea nitrogen and used as a nutrient for seaweed.

As for the humic acid of this embodiment, the fertilizer, soil improvement material, etc. containing humic acid are mentioned, for example. Examples of the humic acid include natural products existing in soil and inland water, or industrial products obtained by oxidative decomposition of young coal such as lignite and lignite. Among these, humic acid as an industrial product is preferable in that stable quality can be obtained and it can be produced in large quantities. As the humic acid, a reaction product of juvenile charcoal and nitric acid and / or sulfuric acid is preferable, and a reaction product of lignite and nitric acid is more preferable.

Humic acid is a polyphenol having a phenolic hydroxyl group in its structure. Humic acid has a repellent effect similar to, for example, cyanamide and calcium oxide. Humic acid has the effect of promoting the growth of seaweed by chelating action with metal elements. Among the metal elements essential for the growth of seaweed, iron is mostly precipitated as hydroxide, so its absorbability by seaweed is low, but its solubility and absorbability are improved by chelating with humic acid.

The humic acid of this embodiment preferably has a melanic index (hereinafter referred to as “MI”) of 2.2 to 3.0, and more preferably 2.2 to 2.4.
Here, MI is an index used for classification of humic acid, and is a ratio of absorbance at wavelengths of 450 nm and 520 nm (A450 / A520) of the absorption spectrum of the sodium hydroxide extract. (Shinichi Kumada, Chemistry of Soil Organic Matter 2nd Academic Publishing Center (1981), Japan Soil Fertilizer Journal No. 71 No. 1 p. 82-85 (2000)).

Specifically, the MI according to the present embodiment is calculated by the following method.
Using a mortar and 250 μm sieve, grind the sample into a 250 μm sieved product. About 10 g of that is taken into a weighing bottle of known mass and weighed accurately. The weighing bottle is left in a dryer maintained at a temperature of 105 ° C. for about 12 hours, and then returned to room temperature in a desiccator and then weighed again. The moisture content of the sample is determined by regarding the reduced mass as moisture. Next, in a 50 ml centrifuge tube, 0.10 g of the above 250 μm sieved product (corresponding to dry mass) and 45 ml of 0.5 mol / L sodium hydroxide aqueous solution are placed and shaken at a room temperature of 20 ° C. for about 1 hour at a speed of 250 rpm. After that, centrifugation at 3,000 × g for about 10 minutes was carried out, and the supernatant was added to Advantech No. Filter through 5C filter paper. The absorbance at 450 nm and the absorbance at 520 nm of the filtrate are measured using distilled water as a blank. In this case, if the absorbance at 450 nm is 1.0 or more, 0.1 mol / L sodium hydroxide aqueous solution is added to adjust the absorbance to 0.8 or more and less than 1.0, and then the absorbance at 520 nm is adjusted. taking measurement. The ratio of (absorbance at 450 nm / absorbance at 520 nm) is calculated and set as MI.

If MI is 2.2 or more, it has sufficient active groups such as alcoholic hydroxyl groups and methoxyl groups, so water solubility is improved. If MI is 3.0 or less, an excessive oxidation reaction will be suppressed and the nitric acid cost will be reduced.
MI can be increased / decreased by increasing / decreasing the amount of nitric acid during the production of crude humic acid, and increasing the amount of nitric acid increases MI.

The humic acid of this embodiment preferably has a weight average molecular weight of 500 to 50,000, more preferably 1000 to 7000.
The weight average molecular weight of humic acid is the value measured by HPSEC method (GPC method) using Waters Alliance HPLC System. SB-803HQ manufactured by SHODEX was used for the column, and sodium polystyrene sulfonate was used for the standard sample. The mobile phase was 10 mmol / L sodium phosphate buffer containing 25% acetonitrile. The detection wavelength is 260 nm.

Humic acid may contain oxidative decomposition products of young coals such as lignite and lignite, and water-soluble salts of humic acids such as magnesium salts, potassium salts, calcium salts, and the like.

The amount of repellent used is preferably 30 to 70 parts by weight with respect to a total of 100 parts by weight of cement and repellent, in order to keep the strength of the concrete structure above a certain level, and to increase the repellent effect on herbivores. 40 to 70 parts by mass are more preferable.
When manufacturing a concrete structure, the amount of water used is preferably 5 to 60 parts by mass, more preferably 8 to 25 parts by mass, and most preferably 10 to 20 parts by mass with respect to 100 parts by mass of the cement and the repellent. preferable.
In the present invention, it is preferable to use an aggregate in terms of improving the effect of preventing the burning and improving the strength of the concrete structure.
Examples of the aggregate include fine aggregate and coarse aggregate. Examples of aggregates include river sand, mountain sand, and crushed stone. The particle size of the aggregate is preferably 0.1 to 20 mm, and more preferably 5 to 13 mm.

When producing a concrete structure, the amount of aggregate used is preferably 50 to 1000 parts by weight, more preferably 200 to 500 parts by weight, and more preferably 300 to 400 parts by weight with respect to 100 parts by weight as a total of cement and repellent. Most preferred. If it is 50 parts by mass or more, the effect of preventing the burning will last for a long time, and if it is 1000 parts by mass or less, the strength of the concrete structure will increase.

In the present embodiment, a concrete structure is produced by mixing and hardening and molding a flame-proofing material. For example, a concrete structure is prepared by mixing and curing and molding at least one of lime nitrogen and humic acid as a repellent material in cement.
The structure of the concrete structure is not particularly limited, but a porous structure is preferable in order to maintain the elution effect of the repellent substance. In order to obtain a porous structure, it is preferable to use an aggregate. Although the shape of a concrete structure is not specifically limited, Shapes, such as a cylinder, a prismatic body, a rectangular parallelepiped, a cone, a sphere, a tetrapot body, are mentioned. The size and shape of the concrete structure is determined according to conditions such as the sea area where it is installed. For example, by combining a plurality of tetrapot bodies in a region where the tidal current is fast, the concrete structure can be prevented from being washed away and can be kept at a target location.

Hereinafter, the present embodiment will be specifically described with experimental examples, but the present embodiment is not limited to these experimental examples.

[Evaluation test of repellent effect]
An evaluation test of the repellent effect was conducted using seaweed as a seaweed as a test material and kitamura sea urchin as a herbivore. Put 6L of artificial seawater (trade name: Instant Ocean Premium, manufactured by Aquarium Systems) into a container (inner length 36.5 cm x inner width 24.3 cm x inner height 8.8 cm). One concrete structure (diameter 10 cm × height 20 cm) was installed. One individual of a 3 cm leaf long seaweed spore and a 30 mm shell diameter sea urchin, transplanted one by one, under culture conditions of a photoperiod such as a temperature of 20 ° C., a light intensity of 90 μmol / m ² / s, a light period of 12 hours and a dark period of 12 hours Cultured for 1 week. The artificial seawater was replaced with a freshly prepared one every 2-3 days. The leaf length of wakame after one week was measured. The leaf length of this seaweed was evaluated as an effect of the repellent.

[Compressive strength evaluation test]
Compressive strength: Based on JIS R 5201-1997 “Physical testing method of cement”, the compressive strength of the concrete structure was measured 7 days after mixing the cement paste and the aggregate.

[Brain specific surface area evaluation test]
Measured according to JIS R 5201-1997 “Cement physical test method”.

[Evaluation test of particle size of lime nitrogen and humic acid]
Measurement was performed using a laser diffraction particle size distribution meter in a dispersed state using an ultrasonic device. LA-920 (Horiba Seisakusho) was used as the model of the ultrasonic device. The average particle size was taken as the particle size.

[Evaluation test of particle size of aggregate]
In accordance with JIS A 1102 “Aggregate Screening Test”, sieving was performed, and the sieve size of the sieve having the highest mass fraction remaining on each sieve was defined as the particle size.

[Comparative Example 1]
Cement (commercially available, ordinary Portland cement, Blaine specific surface area 3300 cm ² / g, cement mineral composition in cement clinker is C ₃ S56 mass%, C ₂ S 26 mass%, C ₃ A 9 mass%, C ₄ AF 9 mass% there. the content of gypsum in the cement is kneaded by introducing a 2.1% by mass) 15 parts by weight 100 parts by weight of tap water as calculated as SO ₃ concrete mixer (Omni mixer, the Chiyoda Machinery Co., Ltd.), A cement paste was prepared. No. 6 crushed stone (product of Itoigawa, Niigata Prefecture, particle size 9.5 mm) as aggregate in cement paste, 340 parts by mass with respect to 100 parts by mass of cement, and further kneaded, a mold with a diameter of 10 cm and a height of 20 cm Poured into the frame. Using a table vibrator (CF-1033, manufactured by Maruto Seisakusho Co., Ltd.), it was compacted at a frequency of 2800 rpm for about 20 seconds, and allowed to stand at room temperature for 24 hours for curing. The above-described evaluation test was carried out using the demolded concrete structure.

[Comparative Example 2]
60 parts by mass of gypsum (commercial product, calcined gypsum), 40 parts by mass of humic acid (commercial product, reaction product of lignite and nitric acid, average particle diameter 2 mm, MI value 2.3, weight average molecular weight 4000), and tap water 15 parts by mass was put into a concrete mixer and kneaded, and was carried out in the same manner as in Comparative Example 1 except that 340 parts by mass of aggregate was added to a total of 100 parts by mass of gypsum and repellent (humic acid). .

[Example 1]
60 parts by mass of cement, 40 parts by mass of lime nitrogen (commercial product, powdered product, CaCN ₂ 50% by mass, average particle size 0.1 mm) and 15 parts by mass of tap water are put into a concrete mixer and kneaded. This was carried out in the same manner as in Comparative Example 1 except that 340 parts by mass of aggregate was added to 100 parts by mass of cement and repellent (lime nitrogen).

[Example 2]
60 parts by mass of cement, 20 parts by mass of lime nitrogen, 20 parts by mass of humic acid, and 15 parts by mass of tap water are put into a concrete mixer and mixed, and the total of cement and repellent materials (lime nitrogen and humic acid) It implemented similarly to the comparative example 1 except having added 340 mass parts of aggregates with respect to 100 mass parts.

[Example 3]
60 parts by mass of cement, 40 parts by mass of humic acid, and 15 parts by mass of tap water are put into a concrete mixer and kneaded, and aggregate 340 parts by mass with respect to a total of 100 parts by mass of cement and repellent (humic acid). This was carried out in the same manner as Comparative Example 1 except that parts were added.

[Example 4]
40 parts by mass of cement, 30 parts by mass of lime nitrogen, 30 parts by mass of humic acid, and 15 parts by mass of tap water are put into a concrete mixer and kneaded to total 100 cement and repellent materials (lime nitrogen and humic acid). It implemented like the comparative example 1 except having added 340 mass parts of aggregates with respect to the mass part.

[Example 5]
40 parts by mass of cement, 30 parts by mass of lime nitrogen, 30 parts by mass of humic acid, and 15 parts by mass of tap water are put into a concrete mixer and kneaded to total 100 cement and repellent materials (lime nitrogen and humic acid). It implemented similarly to the comparative example 1 except having added 50 mass parts of aggregates with respect to the mass part.

The results are shown in Tables 1-2. As shown to the result of Tables 1-2, in the raw material compounding ratio of Examples 1-4 which concern on this embodiment, there is no food damage by a sea urchin by the effect of a repellent, and the leaf length of a seaweed becomes 4.5-6 cm. It was. In Comparative Example 1, since no repellent material was contained, damage by sea urchin was observed, and the leaf length of wakame after one week could not be measured. In Comparative Example 2, since no cement was contained, the damage by sea urchin was observed and the strength was small. By using the aggregate, the leaf length of the seaweed became longer (contrast with Examples 4 to 5).
From the above, in order to obtain a repellent effect, the repellent content is preferably 30 to 70 parts by mass and the aggregate content is 50 to 1000 with respect to 100 parts by mass of cement and repellent. It is preferable to make it a mass part.

The anti-burning material of the present embodiment supplies cyanamide, calcium oxide, and humic acid contained in lime nitrogen to the coastal sea area, and suppresses the feeding pressure (feeding pressure) of the herbivore against seaweed. Cyanamide promotes seaweed growth as a nitrogen source, which is a major component essential for seaweed growth. Humic acid forms a chelate with iron, which is an essential component for seaweed growth, and improves its absorbability and promotes seaweed growth.
According to this embodiment, useful seaweeds such as kombu, wakame, arame, kajime, etc. that have flourished are killed without growing, and the rock surface is exposed or covered with lime algae etc. The phenomenon can be prevented. According to the present embodiment, an effective repellent substance that has a repellent effect on herbivores such as sea urchins and suppresses the food pressure on seaweed can be provided. At the same time, the supply of nitrogen, which is a nutrient for seaweed, can be increased, the iron absorption can be improved, and the growth of seaweed can be promoted. Since the cyanamide and humic acid of this embodiment are biodegradable, this embodiment is free from defects such as cyanamide and humic acid remaining in the environment. It can also be used for improvement. Since the concrete structure of the present embodiment has high strength, it can be installed in water for a long time.
The concrete structure of the present embodiment can be used not only as a repellent supply body but also as an algae growing material.

Claims (8)

Anti-burning material containing cement and repellent. The anti-sunburn material according to claim 1, comprising at least one of lime nitrogen and humic acid as a repellent material. The anti-sunburn material according to claim 1 or 2, wherein the amount of the repellent used is 30 to 70 parts by mass with respect to a total of 100 parts by mass of the cement and the repellent. Furthermore, the anti-burning material according to any one of claims 1 to 3, further comprising an aggregate. The amount of aggregate used is 50 to 1000 parts by mass with respect to 100 parts by mass in total of cement and repellent material. Furthermore, the anti-sunburn material as described in any one of Claims 1-5 containing water. A concrete structure obtained by mixing, curing, and molding the anti-sunburn material according to any one of claims 1 to 5. An anti-sunburn material containing cement and a substance containing at least one of lime nitrogen and humic acid.